Developing new probes for 2DIR spectroscopy

This dissertation presents preliminary work done to characterize new probes for infrared spectroscopy. The probes studied were the C-D stretch transition and the antisymmetric stretch transition of the azide anion. The techniques employed were transient grating spectroscopy and two-dimensional infrared spectroscopy (2DIR). These studies provide information on the lifetime of the chromophores and Fermi Resonances of the chosen oscillators C-D stretch and azide antisymmetric stretch that were observed in the spectra. The first system chosen was a series of deuterated haloforms that include CDCl3, CDBr3 and CDI3. The vibrational lifetime of all three haloforms was measured in a polar solvent, acetone and a nonpolar solvent, benzene. The results were compared to literature values for their undeuterated haloform counterparts. Upon successful completion of the determination of the lifetimes of the deuterated haloforms, we continued the study of the C-D stretch for deuterated formic acid dissolved in hexane. A 2DIR spectrum of the formic acid --d dimer formed in hexane along with a deperturbation calculation determined the coupling constant between the bright state and dark state. The last system studied was the interaction of 3-azopyridine with a strong acid trifluoroacetic acid (TFA), and a weak acid, formic acid once again 2DIR spectroscopy and a deperturbation calculation determined the coupling constant between bright and dark states.